EP2246040A2 - Method for the shaping of hair including a step of applying a reducing composition and a heating step - Google Patents

Abstract

Shaping hair fibers, comprises: (i) applying on the hair fibers a reducing composition comprising one or more cationic polymer, where the weight ratio of reducing composition on the concentration of cationic polymer is 0.1-10 wt.%, and the application is followed by a rinsing; (ii) application of a care composition (II), preferably not rinsed, comprising one or more aminated silicone; and (iii) raising the temperature of the hair fibers using heating means at a temperature of 50-280[deg] C, before or after the optional rinsing of hair fibers.

Description

The present invention relates to a method of treating the hair fibers, as well as to the use of said method.

It is customary, in order to obtain the permanent deformation of the hair, to initially produce the opening of the disulfide bonds of keratin (cystine) with the aid of a composition containing a reducing agent and then, after having preferably rinsed the hair, to reconstitute in a second time said disulfide bonds by applying to the hair smoothed or previously tensioned by suitable means such as hair curlers, an oxidizing composition still called fixer so as to give the hair the desired shape. This technique allows indifferently to achieve either the waving of the hair, or their straightening, creping or smoothing.

The reducing compositions that can be used for carrying out the first step of these processes generally contain thiolated compounds, such as thioglycolic acid, cysteine, cysteamine, thiolactic acid and glycerol monothioglycolate.

The concentration of reducing agents can be very high, often up to 15% by weight of the reducing composition.

Such a technique is not entirely satisfactory. Indeed, this technique is very effective to change the shape of the hair, but also very degrading for hair fibers.

It has furthermore been proposed to raise the temperature of the hair, between the reduction step and the fixing step, by means of a heating iron.

• application sur les fibres capillaires d'une composition réductrice sans céramide, contenant au moins un agent réducteur, le ou les agents réducteurs étant choisis parmi les thiols et représentant moins de 3% en poids du poids total de la composition réductrice si la composition ne contient pas d'aminothiols, et moins de 5% si la composition contient au moins un aminothiol,
• élévation de la température des fibres capillaires, au moyen d'un fer chauffant, à une température au moins égale à 60°C, l'élévation de la température étant effectuée avant ou après le rinçage éventuel des fibres capillaires.

Thus, the patent application EP1584329 discloses a method of treating hair fibers without fixation comprising the steps of:

• application to the hair fibers of a reducing composition without ceramide, containing at least one reducing agent, the reducing agent (s) being chosen from thiols and representing less than 3% by weight of the total weight of the reducing composition if the composition does not contain no aminothiols, and less than 5% if the composition contains at least one aminothiol,
• raising the temperature of the capillary fibers, by means of a heating iron, to a temperature of at least 60 ° C., the rise in temperature being carried out before or after any rinsing of the hair fibers.

However, such a technique leads to a still too inadequate shaping, residual odor problems and requires a careful application of iron.

The problem of the present invention is therefore to provide a method for treating hair fibers that overcomes the disadvantages of the prior art.

In particular, the present invention aims to provide a hair fiber treatment method to change the shape of the hair, control the volume of hair, reduce frizz and improve the cosmetic performance of hair, including the softness, shine and disentangling by better respecting the color of dyed hair.

It is also observed that the method according to the invention facilitates the subsequent blow-drying or straightening of the hair and limits the volume recoveries to 1

Another object of the invention is to provide a method of shaping the hair which brings even more care to the hair, without leaving a residual odor on the latter after its implementation.

The Applicant has found that it is possible to overcome the drawbacks of the prior art and to fulfill the aforementioned objectives, by implementing a process for the treatment of capillary fibers without fixing comprising a step of application to the hair fibers of a reducing composition, containing at least one reducing agent associated with a cationic polymer, then a step of raising the temperature of the capillary fibers, by means of a heating iron, at a temperature of at least 50 ° C., elevation of the temperature being carried out before or after the possible rinsing of the capillary fibers, this process comprising the application of a care composition, preferably not rinsed, comprising one or more amino silicones.

1. (i) application sur les fibres capillaires d'une composition réductrice, comprenant un ou plusieurs polymère cationique, le rapport de la concentration en poids du réducteur sur la concentration en poids du polymère cationique étant compris entre 0,1 et 10, cette application étant suivie d'un rinçage,
2. (ii) application d'une composition de soin, de préférence non rincée, comprenant une ou plusieurs silicone aminée,
3. (iii) élévation de la température des fibres capillaires, à l'aide d'un moyen de chauffage, à une température comprise entre 50 et 280 °C, l'élévation de la température étant effectuée avant ou après le rinçage éventuel des fibres capillaires.

Thus, the subject of the invention is a process for shaping hair fibers comprising the following steps:

1. (i) application to the hair fibers of a reducing composition, comprising one or more cationic polymers, the ratio of the weight concentration of the reducing agent to the concentration by weight of the cationic polymer being between 0.1 and 10, this application being followed by rinsing,
2. (ii) applying a care composition, preferably not rinsed, comprising one or more amino silicones,
3. (iii) raising the temperature of the capillary fibers by means of a heating means to a temperature of between 50 and 280 ° C., the rise in temperature being carried out before or after the possible rinsing of the hair fibers .

Preferably, the ratio of the concentration by weight of the reducing agent to the concentration by weight of the cationic polymer is between 0.5 and 8, and more preferably between 1 and 5.

According to the invention, the term "hair fiber treating method without fixation" discloses a hair fiber treating method not embodying stage attachment other than fixing the air. In particular, this expression means that no fixing step is carried out by means of an oxidizing composition comprising oxygenated water with a hydrogen peroxide content greater than 1% by weight relative to the total weight of the composition (ie 2 volumes), left in contact with the hair for more than 5 minutes.

According to a first embodiment of the process according to the invention, no oxidizing composition is used.

According to a second embodiment of the process according to the invention, a step is implemented comprising the application of an oxidizing composition with a very low concentration of oxygenated water, that is to say comprising hydrogen peroxide. at a content of less than 1% by weight relative to the total weight of the composition (ie 2 volumes) and the composition is allowed to act for less than 5 minutes. This step is useful for neutralizing odors.

REDUCING COMPOSITION

Advantageously, a thiolated reducer is used.

Preferably, the thiol or thiols used as reducing agents in the reducing composition are chosen from aminothiols such as cysteine and its derivatives, such as N-acetylcysteine, cysteamine and its derivatives, preferably its C ₁ -C ₄ acyl derivatives. ₄ such as N-acetyl cysteamine and N-propionyl cysteamine, and non-amino thiols such as thiolactic acid and its esters, such as glycerol monothiolactate, thioglycolic acid and its esters, such as glycerol monothioglycolate or glycol, and thioglycerol.

When the thiol has at least one carboxylic acid function, it is possible to use said thiol as one or more of its salts, such as alkali metal or ammonium salts. It is thus possible to use ammonium thioglycolate as thiol. If the thiol has an amino group, it is possible, where appropriate, to use said thiol in the form of one or more of its salts, such as the aminothiol halides. It is thus possible to use as thiol in the context of the present invention L-cysteine hydrochloride.

As aminothiols that can be used in the reducing composition used according to the invention, mention may also be made of N-mercaptoalkylamides of sugars such as N- (mercapto-2-ethyl) gluconamide, panthetene, N- (mercaptoalkyl) ω- hydroxyalkylamides such as those described in the patent application EP-A-354 835 and N-mono- or N, N-dialkylmercapto 4-butyramides such as those described in the patent application EP-A-368763 aminomercaptoalkylamides such as those described in the patent application EP-A-432000 and alkylaminomercaptoalkylamides such as those described in the patent application EP-A-514282 . Among the non-amino thiols used in the invention, mention may also be made of the mixture of 2-hydroxypropyl thioglycolate (2/3) and 2-hydroxyethyl-1-ethyl thioglycolate (67/33) described in the application patent FR-A-2679448 , β-mercaptopropionic acid and its derivatives, and thiomalic acid.

Preferably, according to the invention, a thiolated reducing agent is used, in particular thioglycolic acid or cysteine.

The total concentration of reducing agent and, in particular, thiols of the reducing compositions of the invention is preferably between 0.1% and 5% relative to the total weight of the composition.

CATIONIC POLYMER

For the purposes of the present invention, the expression "cationic polymer" denotes any polymer containing cationic groups and / or ionizable groups in cationic groups.

The cationic polymers that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in the patent application. EP-A-337354 and in French patents FR-2270846 , 2383660 , 2598611 , 2470596 and 2519863 .

The preferred cationic polymers are chosen from those containing units containing primary, secondary, tertiary and / or quaternary amine groups which may be part of the polymeric backbone or may be supported by a side substituent directly connected thereto. .

The cationic polymers used generally have a number-average molecular weight of between about 500 and 5 × 10 ⁶ , and preferably between about 10 ³ and ³ × 10 ⁶ .

Among the cationic polymers, mention may be made more particularly of the polyamine, polyaminoamide and quaternary polyammonium type polymers.

1. (1) Les homopolymères ou copolymères dérivés d'esters ou d'amides acryliques ou méthacryliques, réticulés ou non, et comportant au moins un des motifs de formules (I), (II), (III) ou (IV) suivantes:
   
   
   dans lesquelles
   R₃ désigne un atome d'hydrogène ou un radical CH₃;
   A représente un groupe alkyle, linéaire ou ramifié, de 1 à 6 atomes de carbone, de préférence 2 ou 3 atomes de carbone ou un groupe hydroxyalkyle de 1 à 4 atomes de carbone ;
   R₄, R₅, R₆, identiques ou différents, représentent un groupe alkyle ayant de 1 à 6 atomes de carbone ou un radical benzyle et de préférence un groupe alkyle ayant de 1 à 6 atomes de carbone ;
   R₁ et R₂, identiques ou différents, représentent hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone et de préférence méthyle ou éthyle ;
   X^- désigne un anion dérivé d'un acide minéral ou organique tel qu'un anion méthosulfate ou un halogénure tel que chlorure ou bromure.

These are known products. They are described in particular in the French patents 2505348 or 2542997 . Among said polymers, mention may be made of:

1. (1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides, crosslinked or otherwise, and comprising at least one of the units of formulas (I), (II), (III) or (IV) following:
   
   
   in which
   R ₃ denotes a hydrogen atom or a CH ₃ radical;
   A represents a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;
   R ₄ , R ₅ , R ₆ , which may be identical or different, represent an alkyl group having from 1 to 6 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms;
   R ₁ and R ₂ , identical or different, represent hydrogen or an alkyl group having 1 to 6 carbon atoms and preferably methyl or ethyl;
   X ^- denotes an anion derived from a mineral or organic acid such as a methosulphate anion or a halide such as chloride or bromide.

• les copolymères d'acrylamide et de diméthylaminoéthyl méthacrylate quaternisé au sulfate de diméthyle ou avec un halogénure de diméthyle, tel que celui vendu sous la dénomination HERCOFLOC par la société HERCULES,
• les copolymères d'acrylamide et de chlorure de méthacryloyloxyéthyl-triméthylammonium décrits par exemple dans la demande de brevet EP-A-080976 et vendus sous la dénomination BINA QUAT P 100 par la société CIBA GEIGY,
• le copolymère d'acrylamide et de méthosulfate de méthacryloyl-oxyéthyltriméthylammonium vendu sous la dénomination RETEN par la société

The polymers of family (1) may also contain one or more unit (s) derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetones acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls (C ₁ -C ₄ ), acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.
Thus, among these polymers of the family (1), mention may be made of:

• copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as that sold under the name HERCOFLOC by the company Hercules,
• the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described for example in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY,
• the copolymer of acrylamide and methacryloyl-oxyethyltrimethylammonium methosulfate sold under the name Reten by the company

HERCULES,

• vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, whether or not quaternized, such as the products sold under the name "GAFQUAT" by the company ISP, for example "GAFQUAT 734" or "GAFQUAT 755" or the products referred to as "COPOLYMER 845, 958 and 937 ". These polymers are described in detail in French patents 2,077,143 and 2,393,573 ,
• dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP,
• the vinylpyrrolidone / methacrylamidopropyldimethylamine copolymers sold in particular under the name STYLEZE CC 10 by ISP,
• quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymers such as the product sold under the name "GAFQUAT HS 100" by the company ISP,
• crosslinked polymers of methacryloyloxyalkyl (C ₁ -C ₄ ) trialkyl (C ₁ -C ₄ ) ammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with quaternized dimethylaminoethyl methacrylate by methyl chloride, the homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. It is more particularly possible to use a crosslinked acrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is marketed under the name "SALCARE® SC 92" by the company CIBA. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names "SALCARE® SC 95" and "SALCARE® SC 96" by the company CIBA.

• (2) cationic polysaccharides chosen in particular from:
  1. a) cellulose ether derivatives containing quaternary ammonium groups described in the French patent 1492597 , and in particular the polymers marketed under denominations "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose reacted with an epoxide substituted by a trimethylammonium group.
  2. b) copolymers of cellulose or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in the patent US 4,131,576 , such as hydroxyalkyl celluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, methacrylmidopropyl trimethylammonium, or dimethyldiallylammonium salt.
     The marketed products corresponding to this definition are more particularly the products sold under the name "Celquat L 200" and "Celquat H 100" by the company National Starch.
  3. c) guar gums containing cationic trialkylammonium groups. For example, guar gums modified with a salt (eg chloride) of 2,3-epoxypropyltrimethylammonium are used.
     Such products are marketed in particular under the trade names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company MEYHALL.
• (3) Polymers consisting of piperazinyl units and straight or branched chain alkylene or hydroxyalkylene divalent radicals, optionally interrupted by oxygen, sulfur, nitrogen or aromatic or heterocyclic rings, as well as oxidation and / or quaternization of these polymers. Such polymers are in particular described in French patents 2,162,025 and 2,280,361 .
• (4) water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides may be crosslinked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or else by an oligomer resulting from the reaction of a bifunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halogenide, epilhalohydrin, diepoxide or bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 moles per amine group of the polyaminoamide; these polyaminoamides can be alkylated or if they comprise one or more tertiary amino functions, quaternized. Such polymers are in particular described in French patents 2,252,840 and 2,368,508 .
• (5) Polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid-dialkylamino hydroxyalkyldialkylenetriamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in the French patent 1,583,363 .
  Among these derivatives, mention may be made more particularly of the adipic acid / dimethylaminohydroxypropyl / diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz.
• (6) Polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 6 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid is between 0.8: 1 and 1.4: 1; the polyaminoamide resulting therefrom being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are described in particular in the patents US 3,227,615 and 2,961,347. Polymers of this type are in particular sold under the name "Hercosett 57" by the company Hercules Inc. or under the name "PD 170" or "Delsette 101" by the company Hercules in the case of the adipic acid copolymer epoxypropyl / diethylenetriamine.
• (7) cyclopolymers of alkyl diallyl amine or of dialkyl diallyl ammonium, such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (V) or (VI):
  
  
  formulas in which
  k and t are equal to 0 or 1, the sum k + t being equal to 1;
  R ₉ denotes a hydrogen atom or a methyl radical;
  R ₇ and R ₈ , independently of each other, denote an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group. (C ₁ -C ₄ ), or R ₇ and R ₈ may designate, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R ₇ and R _8, independently of one another, preferably denote an alkyl group having from 1 to 4 carbon atoms;
  Y ^- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are in particular described in the French patent 2,080,759 and in its certificate of addition 2,190,406.

• (8) Le polymère de diammonium quaternaire contenant des motifs récurrents répondant à la formule (VII) :
  
  formule (VII) dans laquelle :
  R₁₀, R₁₁, R₁₂ et R₁₃, identiques ou différents, représentent des radicaux aliphatiques, alicycliques, ou arylaliphatiques contenant de 1 à 6 atomes de carbone ou des radicaux hydroxyalkylaliphatiques inférieurs, ou bien R₁₀, R₁₁, R₁₂ et R₁₃, ensemble ou séparément, constituent avec les atomes d'azote auxquels ils sont rattachés des hétérocycles contenant éventuellement un second hétéroatome autre que l'azote ou bien R₁₀, R₁₁, R₁₂ et R₁₃ représentent un radical alkyle en C₁-C₆, linéaire ou ramifié, substitué par un groupement nitrile, ester, acyle, amide ou -CO-O-R₁₄-D ou -CO-NH-R₁₄-D où R₁₄ est un alkylène et D un groupement ammonium quaternaire ;
  A1 et B1 représentent des groupements polyméthyléniques contenant de 2 à 20 atomes de carbone pouvant être linéaires ou ramifiés, saturés ou insaturés, et pouvant contenir, liés à ou intercalés dans la chaîne principale, un ou plusieurs cycles aromatiques, ou un ou plusieurs atomes d'oxygène, de soufre ou des groupements sulfoxyde, sulfone, disulfure, amino, alkylamino, hydroxyle, ammonium quaternaire, uréido, amide ou ester, et
  X^- désigne un anion dérivé d'un acide minéral ou organique ;
  A1, R₁₀ et R₁₂ peuvent former avec les deux atomes d'azote auxquels ils sont rattachés un cycle pipérazinique ; en outre si A1 désigne un radical alkylène ou hydroxyalkylène linéaire ou ramifié, saturé ou insaturé, B1 peut également désigner un groupement
  
          -(CH₂)_n-CO-D-OC-(CH₂)n-
  
  dans lequel n est compris entre 1 et 100 et de préférence entre 1 et 50, et D désigne :
  1. a) un reste de glycol de formule : -O-Z-O-, où Z désigne un radical hydrocarboné linéaire ou ramifié ou un groupement répondant à l'une des formules suivantes :
     
             -(CH₂-CH₂-O)_x-CH₂-CH₂-
     
             -[CH₂-CH(CH₃)-O]_y-CH₂-CH(CH₃)-
     
     où x et y désignent un nombre entier de 1 à 4, représentant un degré de polymérisation défini et unique ou un nombre quelconque de 1 à 4 représentant un degré de polymérisation moyen ;
  2. b) un reste de diamine bis-secondaire tel qu'un dérivé de pipérazine ;
  3. c) un reste de diamine bis-primaire de formule : -NH-Y-NH-, où Y désigne un radical hydrocarboné linéaire ou ramifié, ou bien le radical bivalent
     
             -CH₂-CH₂-S-S-CH₂-CH₂- ;
     
     
  4. d) un groupement uréylène de formule : -NH-CO-NH- .

De préférence, X- est un anion tel que le chlorure ou le bromure.Among the polymers defined above, mention may be made more particularly of the homopolymer of dimethyldiallyl ammonium chloride sold under the name "Merquat 100" by Calgon (and its counterparts of low weight average molecular weight) and the chloride copolymers diallyldimethylammonium and acrylamide sold under the name "MERQUAT 550".

• (8) The quaternary diammonium polymer containing recurring units corresponding to formula (VII):
  
  formula (VII) in which:
  R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 6 carbon atoms or lower hydroxyalkylaliphatic radicals, or R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ represent a C ₁ alkyl radical; -C ₆ , linear or branched, substituted with a nitrile, ester, acyl, amide group or -CO-OR ₁₄ -D or -CO-NH-R ₁₄ -D where R ₁₄ is an alkylene and D a quaternary ammonium group;
  A1 and B1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more carbon atoms; oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
  X ^- denotes an anion derived from a mineral or organic acid;
  A1, R ₁₀ and R ₁₂ may form with the two nitrogen atoms to which they are attached a piperazine ring; in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also designate a group
  
  - (CH ₂ ) _n -CO-D-OC- (CH ₂ ) n-
  
  in which n is between 1 and 100 and preferably between 1 and 50, and D is:
  1. a) a glycol residue of formula: -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas:
     
     - (CH ₂ -CH ₂ -O) _x -CH ₂ -CH ₂ -
     
     - [CH ₂ -CH (CH ₃ ) -O] _y -CH ₂ -CH (CH ₃ ) -
     
     where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;
  2. b) a bis-secondary diamine residue such as a piperazine derivative;
  3. c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or the divalent radical
     
     -CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -;
     
     
  4. d) a ureylene group of formula: -NH-CO-NH-.

Preferably, X- is an anion such as chloride or bromide.

dans laquelle R₁₀, R₁₁, R₁₂ et R₁₃, identiques ou différents, désignent un radical alkyle ou hydroxyalkyle ayant de 1 à 4 atomes de carbone environ,
n et p sont des nombres entiers variant de 2 à 20 environ et,
X^- est un anion dérivé d'un acide minéral ou organique.

• (9) Les polymères de polyammonium quaternaire constitués de motifs de formule (IX) :
  
  dans laquelle :
  p désigne un nombre entier variant de 1 à 6 environ,
  D peut être nul ou peut représenter un groupement
  • (CH₂)_r-CO- dans lequel r désigne un nombre égal à 4 ou à 7, et
  X^- est un anion dérivé d'un acide minéral ou organique.

Les polymères cationiques comportant des motifs de formule (IX) sont notamment décrits dans la demande de brevet EP-A-122 324 et peuvent être préparés selon les procédés décrits dans les brevets U.S.A. n° 4 157 388 , 4 390 689 , 4 702 906 , 4 719 282 .
Parmi ces polymères, on préfère ceux de masse moléculaire mesurée par RMN du Carbone 13 inférieure à 100000, et dans la formule de laquelle :
p est égal à 3, et,

1. a) D représente un groupement -(CH₂)₄-CO- , X désigne un atome de chlore, la masse moléculaire mesurée par RMN du Carbone 13 (RMN¹³C) étant d'environ 5600 ; un polymère de ce type est proposé par la société MIRANOL sous le nom de MIRAPOL-AD1,
2. b) D représente un groupement -(CH₂)₇-CO-, X désigne un atome de chlore, la masse moléculaire mesurée par RMN du Carbone 13 (RMN¹³C) étant d'environ 8100 ; un polymère de ce type est proposé par la société MIRANOL sous le nom de MIRAPOL-AZ1,
3. c) D désigne la valeur zéro, X désigne un atome de chlore, la masse moléculaire mesurée par RMN du Carbone 13, ( RMN¹³C) étant d'environ 25500 ; un polymère de ce type est vendu par la société MIRANOL sous le nom MIRAPOL-A15,
4. d) un " Block Copolymer " formé de motifs correspondant aux polymères décrits aux alinéas a) et c), proposé par la société MIRANOL sous les noms MIRAPOL-9, (masse moléculaire RMN¹³C, environ 7800) MIRAPOL-175, (masse moléculaire RMN¹³C, environ 8000) MIRAPOL-95, (masse moléculaire RMN¹³C, environ 12500).

These polymers have a number average molecular weight generally between 1000 and 100000.
Polymers of this type are in particular described in French patents 2,320,330 , 2270846 , 2316271 , 2336434 and 2413907 and patents US2,273,780 , 2375853 , 2388614 , 2454547 , 3206462 , 2261002 , 2271378 , 3874870 , 4001432 , 3929990 , 3966904 , 4005193 , 4025617 , 4025627 , 4025653 , 4026945 and 4027020 .
It is more particularly possible to use polymers which consist of recurring units corresponding to the following formula (VIII):

in which R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , which may be identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms,
n and p are integers ranging from about 2 to about 20 and,
X ^- is an anion derived from a mineral or organic acid.

• (9) Quaternary polyammonium polymers consisting of units of formula (IX):
  
  in which :
  p denotes an integer ranging from 1 to about 6,
  D may be zero or may represent a group
  • (CH ₂ ) _r -CO- wherein r denotes a number equal to 4 or 7, and
  X ^- is an anion derived from a mineral or organic acid.

The cationic polymers comprising units of formula (IX) are described in particular in the patent application EP-A-122,324 and can be prepared according to the processes described in the patents USA No. 4,157,388 , 4,390,689 , 4,702,906 , 4,719,282 .
Among these polymers, those with a molecular weight measured by 13C NMR of less than 100,000 are preferred, and in the formula of which:
p is 3, and,

1. a) D represents a - (CH _{2) 4} -CO-, X denotes a chlorine atom, the molecular mass, measured by carbon 13 NMR ⁽¹³ C NMR) being about 5600; a polymer of this type is proposed by MIRANOL under the name MIRAPOL-AD1,
2. b) D represents a group - (CH ₂ ) ₇ -CO-, X denotes a chlorine atom, the molecular weight measured by NMR of Carbon 13 ( ¹³ C NMR) being approximately 8100; a polymer of this type is proposed by MIRANOL under the name MIRAPOL-AZ1,
3. c) D denotes the value zero, X denotes a chlorine atom, the molecular weight measured by NMR of Carbon 13, ( ¹³ C NMR) being approximately 25500; a polymer of this type is sold by MIRANOL under the name MIRAPOL-A15,
4. d) a "Block Copolymer" formed by units corresponding to the polymers described under (a) and (c), proposed by MIRANOL under the trade names MIRAPOL-9, (molecular weight ¹³ C NMR, approximately 7800) MIRAPOL-175, (mass ¹³ C NMR, about 8000) MIRAPOL-95, ( ¹³ C NMR molecular weight, about 12500).

• (10) Les polymères quaternaires de vinylpyrrolidone et de vinylimidazole tels que par exemple les produits commercialisés sous les dénominations Luviquat FC 905, FC 550 et FC 370 par la société B.A.S.F.
• (11) Les polyamines comme le Polyquart H vendu par HENKEL, référencé sous le nom de " POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE " dans le dictionnaire CTFA.

Even more particularly, according to the invention, the patterned polymer of formula (XI) in which p is equal to 3, D denotes the value zero, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13, ( ¹³ C NMR) being about 25500.

• (10) Quaternary polymers of vinylpyrrolidone and vinylimidazole such as, for example, the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company BASF
• (11) Polyamines such as Polyquart H sold by HENKEL, referenced under the name "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary.

Other cationic polymers that may be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.

Among all the cationic polymers that may be used in the context of the present invention, it is preferred to use the polymers of families (7) and (8).

The cationic polymer (s) according to the invention is (are) in an amount of from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, relative to the total weight of the composition.

Preferably, the cationic polymers are chosen from hexadimethrin chloride and homo or copolymers of dimethyldiallylammonium chloride.

Advantageously, the pH of the reducing composition is between 4 and 12, preferably between 7 and 11.

The pH adjustment of the composition can be obtained using an alkaline agent, such as, for example, ammonia, organic amines such as monoethanolamine, diethanolamine, triethanolamine, 1,3-propanediamine and 2-amino-2-methylpropanol, 2-methyl-1-aminopropanol, an alkaline or ammonium carbonate or bicarbonate, an organic carbonate such as guanidine carbonate, an alkaline hydroxide, such as sodium hydroxide, or using an acidifying agent such as for example hydrochloric acid, acetic acid, lactic acid, oxalic acid or boric acid.

The reducing composition generally comprises one or more cosmetically acceptable solvents, preferably chosen from water, C ₁ -C ₆ alcohols, preferably alkanols such as ethanol, propanol and isopropanol, polyols such as propylene glycol, pentanediol and glycerin and hexylene glycol, benzyl alcohol, polyol ethers, C ₂ -C ₆ esters, N-methylpyrrolidone (NMP), and C ₃ -C ₃ ketones ₆ .

In order to improve the properties of the hair compositions according to the invention, the reducing composition used according to the invention may also comprise one or more cosmetic additives.

This or these cosmetic additives are generally chosen from volatile or nonvolatile silicones, linear or cyclic, nonionic, anionic or amphoteric polymers, in soluble or insoluble form such as latices, peptides and their derivatives, protein hydrolysates, waxes, swelling agents and penetration or to enhance the effectiveness of the reducing agent such as SiO ₂ / polydimethylsiloxane mixture, dimethylisosorbitol, urea and its derivatives, anionic surfactants, cationic, no ionic, amphoteric or zwitterionic agents, anti-hair loss agents, anti-dandruff agents, natural or synthetic, associative or non-associative thickeners, suspending agents, sequestering agents, opacifying agents, dyes, sunscreens, vitamins or provitamins, fatty acids, fatty alcohols, mineral, vegetable or synthetic oils, mineral particles, as well as perfumes and preservatives, and mixtures thereof.

The cosmetic active agent (s) may be chosen from silicones.

As silicones that may be used as cosmetic active agents in the process according to the invention, mention may be made of polydimethylsiloxanes and quaternized polyorganosiloxanes such as those described in the French patent application. FR 2535730 polyorganosiloxanes containing aminoalkyl groups modified with alkoxycarbonylalkyl groups such as those described in the patent US 4,749,732 polyorganosiloxanes such as the polydimethylsiloxane-polyoxyalkyl copolymer of the dimethicone copolyol type, a polydimethylsiloxane containing stearoxy end groups (stearoxydimethicone), a polydimethylsiloxane-dialkylammonium acetate copolymer or a polydimethylsiloxane polyalkylbetaine copolymer described in the British patent. GB 2197352 organopolysiloxanes modified with mercapto or mercaptoalkyl groups such as those described in the French patent FR 1530369 and in the European patent application EP 295780 .

Moreover, the cosmetic active agent (s) may also be chosen from fatty acids and fatty alcohols.

As fatty acids that can be used as active agents in the process according to the invention, mention may especially be made of C ₈ -C ₃₀ carboxylic acids, such as palmitic acid, oleic acid, linoleic acid and myristic acid. stearic acid, lauric acid, and mixtures thereof.

As fatty alcohols that may be used in the present invention, mention may be made especially of C ₈ -C ₃₀ alcohols, for example palmitic, oleyl, linoleyl, myristyl, stearyl and lauryl alcohols or mixtures thereof.

The reducing composition used in the process according to the invention may be in the form of a lotion, thickened or not, a cream, a gel, or a foam.

After the application of the reducing composition, said composition may be left, generally for 5 to 60 minutes, preferably 5 to 30 minutes, optionally under a helmet.

CARE COMPOSITION (ii)

In what follows or which precedes, is meant by silicone or polysiloxane, in accordance with the general acceptance, any organosilicon polymer or oligomer with a linear or cyclic structure, branched or crosslinked, of variable molecular weight, obtained by polymerization and / or or polycondensation of suitably functionalized silanes, and essentially constituted by a repetition of main units in which the silicon atoms are connected to each other by oxygen atoms (silSi-O-Si≡ siloxane bond), optionally substituted hydrocarbon radicals being directly bonded by the intermediate of a carbon atom on said silicon atoms. The most common hydrocarbon radicals are alkyl radicals, especially C ₁ -C ₁₀ and in particular methyl radicals, fluoroalkyl radicals, aryl radicals and in particular phenyl radicals, and alkenyl radicals and in particular vinyl radicals; other types of radicals which may be bonded either directly or via a hydrocarbon radical to the siloxane chain include hydrogen, halogens and in particular chlorine, bromine or fluorine, thiols, alkoxy radicals, polyoxyalkylene (or polyether) radicals and in particular polyoxyethylene and / or polyoxypropylene radicals, hydroxyl or hydroxyalkyl radicals, amide groups, acyloxy or acyloxyalkyl radicals, amphoteric or betaine groups, anionic groups such as carboxylates , thioglycolates, sulfosuccinates, thiosulphates, phosphates and sulphates, this list being of course in no way limiting ("organomodified" silicones).

1. (a) les polysiloxanes répondant à la formule :
   
   dans laquelle x' et y' sont des nombres entiers dépendant du poids moléculaire, généralement tels que ledit poids moléculaire moyen en poids est compris entre 5000 et 500000 environ ;
   R₁, R₂, R₃ identiques ou différents désignent un radical hydroxyle, un radical alkyle en C₁ à C₄, un radical alcoxy en C₁ à C₄, phényle ;
   X désigne un radical alkylène en C₁-C₄, ramifié ou non ;
   R₄ désigne un radical alkyle en C₁-C₄ ou phényle ;
   p, p' désignent indépendamment l'un de l'autre un nombre entier variant de 1 à 10.

According to the invention, aminosilicone used in step (ii) denotes any silicone comprising at least one primary, secondary, tertiary amine or a quaternary ammonium group. We can quote:

1. (a) polysiloxanes having the formula:
   
   wherein x 'and y' are molecular weight dependent integers, generally such that said weight average molecular weight is from about 5,000 to about 500,000;
   R _1, R _2, R _3, identical or different, denote a hydroxyl radical, an alkyl radical in C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl, phenyl;
   X denotes an alkylene radical C ₁ -C ₄ alkyl, branched or unbranched;
   R ₄ denotes a C ₁ -C ₄ alkyl radical or phenyl radical;
   p, p 'denote independently of one another an integer ranging from 1 to 10.

Preferably, alkyl is methyl and alkoxy is methoxy.

Preferably, p = 3, p '= 2 and R4 is methyl and X is methylene.

• (b) les silicones aminées répondant à la formule :
  
  dans laquelle
  R₅ représente un radical hydrocarboné monovalent ayant de 1 à 18 atomes de carbone, et en particulier un radical alkyle en C₁-C₁₈, ou alcényle en C₂-C₁₈, par exemple méthyle ;
  R₆ représente un radical hydrocarboné divalent, notamment un radical alkylène en C₁-C₁₈ ou un radical alkylèneoxy divalent en C₁-C₁₈, par exemple en C₁-C₈ relié au Si par une liaison SiC;
  Q^- est un anion tel qu'un ion halogénure, notamment chlorure ou un sel d'acide organique (acétate ...);
  r représente une valeur statistique moyenne de 2 à 20 et en particulier de 2 à 8 ;
  s représente une valeur statistique moyenne de 20 à 200 et en particulier de 20 à 50.
  De telles silicones aminées sont décrites plus particulièrement dans le brevet US 4185087 .
  Une silicone entrant dans cette classe est la silicone commercialisée par la société Union Carbide sous la dénomination "Ucar Silicone ALE 56.
• c) les silicones ammonium quaternaire de formule :
  
  dans laquelle
  R₇, identiques ou différents, représentent un radical hydrocarboné monovalent ayant de 1 à 18 atomes de carbone, et en particulier un radical alkyle en C₁-C₁₈, un radical alcényle en C₂-C₁₈ ou un cycle comprenant 5 ou 6 atomes de carbone, par exemple méthyle ;
  R₆ représente un radical hydrocarboné divalent, notamment un radical alkylène en C₁-C₁₈ ou un radical alkylèneoxy divalent en C₁-C₁₈, par exemple en C₁-C₈ relié au Si par une liaison SiC;
  R₈, identiques ou différents, représentent un atome d'hydrogène, un radical hydrocarboné monovalent ayant de 1 à 18 atomes de carbone, et en particulier un radical alkyle en C₁-C₁₉, un radical alcényle en C₂-C₁₈, un radical -R₆-NHCOR₇ ;
  X- est un anion tel qu'un ion halogénure, notamment chlorure ou un sel d'acide organique (acétate ...);
  r représente une valeur statistique moyenne de 2 à 200 et en particulier de 5 à 100 ;
  Ces silicones sont par exemple décrites dans la demande EP-A-0530974 .
  Selon l'invention, on préfère utiliser une silicone aminée:
  • dont l'indice d'amine est supérieur à 0,15 meq par gramme,
  • possédant des extréminés hydroxy et/ou alcoxy.

Among these polymers, mention may be made of the compounds designated by the name "amodimethicone" and "trimethylsilylaminodimethicone" in the CTFA dictionary.

• (b) amino silicones corresponding to the formula:
  
  in which
  R ₅ represents a monovalent hydrocarbon radical having 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₈ alkyl or C ₂ -C ₁₈ alkenyl radical, for example methyl;
  R ₆ represents a divalent hydrocarbon radical, in particular a C ₁ -C ₁₈ alkylene radical or a divalent C ₁ -C ₁₈ , for example C ₁ -C _8, alkyleneoxy radical connected to Si by an SiC bond;
  Q ^- is an anion such as a halide ion, especially chloride or an organic acid salt (acetate, etc.);
  r represents an average statistical value of 2 to 20 and in particular 2 to 8;
  s represents an average statistical value of 20 to 200 and in particular of 20 to 50.
  Such amino silicones are described more particularly in the patent US 4185087 .
  A silicone in this class is the silicone marketed by Union Carbide under the name Ucar Silicone ALE 56.
• c) quaternary ammonium silicones of formula:
  
  in which
  R ₇ , which may be identical or different, represent a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₈ alkyl radical, a C ₂ -C ₁₈ alkenyl radical or a 5 or 6-membered ring; carbon atoms, for example methyl;
  R ₆ represents a divalent hydrocarbon radical, in particular a C ₁ -C ₁₈ alkylene radical or a divalent C ₁ -C ₁₈ , for example C ₁ -C _8, alkyleneoxy radical connected to Si by an SiC bond;
  R ₈ , which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon radical containing from 1 to 18 carbon atoms, and in particular a C ₁ -C ₁₉ alkyl radical or a C ₂ -C ₁₈ alkenyl radical, a radical -R ₆ -NHCOR ₇ ;
  X - is an anion such as a halide ion, especially chloride or an organic acid salt (acetate, etc.);
  r represents an average statistical value of 2 to 200 and in particular 5 to 100;
  These silicones are for example described in the application EP-A-0530974 .
  According to the invention, it is preferred to use an amino silicone:
  • whose amine number is greater than 0.15 meq per gram,
  • having extramines hydroxy and / or alkoxy.

By way of example, mention may be made, as a microemulsion, containing such a silicone, the product marketed by WACKER under the name WACKER-BELSIL ADM LOG 1.

The amino silicones can be in the form of microemulsion.

Advantageously, the aminosilicone concentration in the pretreatment or post-treatment composition is between 0.05 and 10% by weight relative to the total weight of this composition, and more advantageously between 0.1 and 7%. .

The care compositions containing the amino silicones may contain water-soluble or liposoluble active agents, having a cosmetic activity. Examples of active ingredients include vitamins and their derivatives such as vitamin E, vitamin E acetate, vitamin C and its esters, vitamin B, vitamin A alcohol or retinol, vitamin E vitamin A acid or retinoic acid and its derivatives, provitamins such as panthenol, vitamin A palmitate, niacinamide, ergocalciferol, antioxidants, essential oils, humectants, silicone or non-silicone sunscreens, agents preservatives, sequestering agents, pearlescent agents, pigments, moisturizing agents, anti-dandruff agents, antiseborrhoeic agents, plasticizers, hydroxy acids, electrolytes and perfumes. Skincare compositions containing the amino silicones may contain one or more of the additives listed for the reducing compositions.

Preferably, the pH of the aminated silicone composition is preferably between 2 and 10, and more preferably between 3 and 9.

Such care compositions are described in SP1 247 518.

HEATING STEP

As explained above, the method according to the invention comprises a step of raising the temperature of the hair fibers, using a heating means.

As heating means, it is possible to use a helmet, a hair dryer, an iron with or without the addition of steam, especially as described in FR 2921805 , an infrared device.

The heating step may be preceded by a pre-drying step, using one or more heating means.

For the purposes of the present invention, the term "iron" means a device for heating the capillary fibers by contact.

The end of the iron coming into contact with the hair can have different shapes. It may in particular have a flat surface; in this case we speak of flat iron. It can also have a rounded surface; in this case we speak of round iron.

The application of iron can be done by successive separate keys of a few seconds, or by moving or sliding progressively along the wicks.

By way of example of iron that can be used in the process according to the invention, mention may be made of all types of flat or round iron and, in particular, in a nonlimiting manner, those described in the patents. US 4103145 , US 4308878 , US 5983903 , US 5957140 , US 5494058 and US 5046516 .

Preferably, the temperature of the hair fibers is raised to a temperature between 60 ° C and 250 ° C, more preferably between 120 ° C and 220 ° C.

In the case of using a helmet or a hair dryer, the drying time can vary from 1 to 90 minutes.

• Variante 1 : étape i, puis étape ii puis étape iii,
• Variante 2 : étape ii, puis étape i puis étape iii,
• Variante 3 : étape ii, puis étape i puis étape ii puis étape iii.

The order of steps (i), (ii) and (iii) is indifferent. Preferably, the method of the invention can be illustrated by the following variants:

• Variant 1: step i, then step ii then step iii,
• Variant 2: step ii, then step i then step iii,
• Variant 3: step ii, then step i then step ii and then step iii.

Step ii may optionally be followed by rinsing or shampooing, preferably, step ii is not rinsed. If step ii is followed by rinsing, the exposure time before rinsing is between 30 seconds and 10 minutes.

POSSIBLE ADDITIONAL STEPS Application of a care composition (iv)

The method according to the invention may further comprise the application of a care composition (iv) different from the care composition (ii). This composition comprises at least one silicone or non-silicone fatty substance.

The fatty substances that can be used in the care compositions (iv) according to the present invention are all oils, waxes, silicone resins or not, organic or mineral, natural or synthetic.

An oil, within the meaning of the present invention, is a lipophilic compound, liquid at room temperature (about 25 ° C), solid state change / reversible liquid. Animal and vegetable oils comprise essential components of propane-1,2,3-triol triesters.

A wax, within the meaning of the present invention, is a lipophilic compound, solid at room temperature (about 25 ° C.), with a reversible solid / liquid state change, having a melting temperature greater than about 40 ° C. and that can go up to 200 ° C, and having in the solid state an anisotropic crystalline organization.

NON SILICONE BODIES

• les huiles hydrocarbonées d'origine animale, telles que le perhydrosqualène ;
• les huiles hydrocarbonées d'origine végétale, telles que les triglycérides liquides d'acides gras comportant de 4 à 10 atomes de carbone comme les triglycérides des acides heptanoïque ou octanoïque ou encore, par exemple les huiles de tournesol, de maïs, de soja, de courge, de pépins de raisin, de sésame, de noisette, d'abricot, de macadamia, d'arana, de tournesol, de ricin, d'avocat, les triglycérides des acides caprylique/caprique comme par exemple ceux vendus par la société Stearineries Dubois ou ceux vendus sous les dénominations Miglyol 810, 812 et 818 par la société Dynamit Nobel, l'huile de jojoba, l'huile de beurre de karité ;
• les esters et les éthers de synthèse, notamment d'acides gras, comme les huiles de formules R⁶COOR⁷ et R⁶OR⁷ dans laquelle R⁶ représente le reste d'un acide gras comportant de 8 à 29 atomes de carbone, et R⁷ représente une chaîne hydrocarbonée, ramifiée ou non, contenant de 3 à 30 atomes de carbone, comme par exemple l'huile de Purcellin, l'isononanoate d'isononyle, le myristate d'isopropyle, le palmitate d'éthyl-2-hexyle, le stéarate d'octyl-2-dodécyle, l'érucate d'octyl-2-dodécyle, l'isostéarate d'isostéaryle ; les esters hydroxylés comme l'isostéaryl lactate, l'octylhydroxystéarate, l'hydroxystéarate d'octyldodécyle, le diisostéaryl-malate, le citrate de triisocétyle, les heptanoates, octanoates, décanoates d'alcools gras ; les esters de polyol, comme le dioctanoate de propylène glycol, le diheptanoate de néopentylglycol et le diisononaoate de diéthylèneglycol ; et les esters de pendaérythritol comme le tétraisostéarate de pentaérythrityle ;

• les hydrocarbures linéaires ou ramifiés, d'origine minérale ou synthétique, tels que les huiles de paraffine, volatiles ou non, et leurs dérivés, la vaseline, les polydécènes, le polyisobutène hydrogéné tel que l'huile de parléam ;
• les alcools gras fluides ayant de 8 à 26 atomes de carbone, comme l'octyldodécanol, le 2-butyloctanol, l'alcool oléique, l'alcool linoléique ou l'alcool linolénique ;
• les alcools gras alcoxylés et notamment éthoxylés tels que l'oleth-12 ;
• les huiles fluorées partiellement hydrocarbonées comme celles décrites dans le document JP-A-2 295912 . Comme huiles fluorées, on peut citer aussi le perfluorométhylcyclopentane et le perfluoro-1,3- diméthylcyclohexane, par exemple vendus sous les dénominations de « FLUTEC PC1® » et « FLUTEC PC3® » par la Société BNFL Fluorochemicals ; le perfluoro-1,2-diméthylcyclobutane ; les perfluoralcanes tels que le dodécafluoropentane et le tétradécafluorohexane, par exemple vendus sous les dénominations de « PF 5050® » et « PF 5060® » par la Société 3M, ou encore le bromoperfluorooctyle par exemple vendu sous la dénomination « FORALKYL® » par la Société Atochem ; le nanofluorométhoxybutane par exemple vendu sous la dénomination « MSX 4518® » par la Société 3M et le nanofluoroéthoxyisobutane ; les dérivés de perfluoromorpholine, tels que la 4-trifluorométhyl perfluoromorpholine par exemple vendue sous la dénomination « PF 5052® » par la Société 3M.

As oils that can be used in the composition of the invention, mention may be made for example of:

• hydrocarbon oils of animal origin, such as perhydrosqualene;
• hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn, soybean, squash, grape seed, sesame, hazelnut, apricot, macadamia, arana, sunflower, castor oil, avocado, triglycerides of caprylic / capric acids, for example those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil;
• esters and synthetic ethers, in particular of fatty acids, such as the oils of formulas R ⁶ COOR ⁷ and R ⁶ OR ⁷ in which R ⁶ represents the residue of a fatty acid comprising from 8 to 29 carbon atoms, and R ⁷ represents a hydrocarbon chain, branched or unbranched, containing from 3 to 30 carbon atoms, for example Purcellin oil, isononyl isononanoate, isopropyl myristate or ethyl-2- palmitate; hexyl, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and sodium diisononate diethylene glycol; and pendaerythritol esters such as pentaerythrityl tetraisostearate;

• linear or branched hydrocarbons of mineral or synthetic origin, such as paraffin oils, volatile or not, and derivatives thereof, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam oil;
• fluid fatty alcohols having from 8 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, oleic alcohol, linoleic alcohol or linolenic alcohol;
• alkoxylated and especially ethoxylated fatty alcohols such as oleth-12;
• partially hydrocarbon-based fluorinated oils such as those described in the document JP-A-2 295912 . As fluorinated oils, mention may also be made of perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, for example sold under the names "FLUTEC PC1®" and "FLUTEC PC3®" by BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, for example sold under the names "PF 5050®" and "PF 5060®" by the company 3M, or bromoperfluorooctyl for example sold under the name "FORALKYL®" by the Company Atochem; nanofluoromethoxybutane, for example sold under the name "MSX 4518®" by the company 3M and nanofluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine, for example sold under the name "PF 5052®" by the company 3M.

The term "hydrocarbon-based oil" in the list of oils mentioned above, any oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and / or alcohol groups.

Animal and vegetable waxes comprise, as essential components, esters of carboxylic acids and long-chain alcohols. In general, the size of the crystals of the wax is such that the crystals diffract and / or diffuse the light, conferring on the composition which comprises them a more or less opaque cloudy appearance. By bringing the wax to its melting temperature, it is possible to render it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, a recrystallization of the wax in the oils of the mixture, detectable microscopically and macroscopically (opalescence).

As waxes that can be used in the present invention, mention may be made of waxes of animal origin, such as beeswax, spermaceti, lanolin wax and lanolin derivatives; vegetable waxes such as sunflower wax, rice wax, apple wax, Carnauba wax, Candelilla wax, Ouricury wax, Japan wax, cocoa butter wax or cork fiber wax or sugar cane wax; mineral waxes, for example paraffin, petrolatum, lignite or waxes microcrystallines, ceresin or ozokerite; synthetic waxes such as polyethylene waxes, Fischer-Tropsch waxes, and mixtures thereof.

SILICONE BODY

It is also possible to use, in the care composition (iv) according to the invention, a silicone as a fatty substance.

The silicones that can be used in the compositions according to the present invention can be linear, cyclic, branched or unbranched, volatile or nonvolatile. They may be in the form of oils, resins or gums, they may in particular be polyorganosiloxanes insoluble in the cosmetically acceptable medium.

Organopolysiloxanes are defined in more detail in Walter NOLL "Chemistry and Technology of Silicones" (1968) Academic Press . They can be volatile or non-volatile.

1. (i) les silicones cycliques comportant de 3 à 7 atomes de silicium et, de préférence, 4 à 5. Il s'agit, par exemple, de l'octaméthylcyclotétra-siloxane commercialisé notamment sous le nom de "VOLATILE SILICONE 7207" par UNION CARBIDE ou "SILBIONE 70045 V 2" par RHODIA, le décaméthylcyclopentasiloxane commercialisé sous le nom de "VOLATILE SILICONE 7158" par UNION CARBIDE, "SILBIONE 70045 V 5" par RHODIA, ainsi que leurs mélanges.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and more particularly between:

1. (i) cyclic silicones containing from 3 to 7 silicon atoms and, preferably, from 4 to 5. It is, for example, octamethylcyclotetrasiloxane marketed in particular under the name "VOLATILE SILICONE 7207" by UNION CARBIDE or "SILBIONE 70045 V 2" by RHODIA, decamethylcyclopentasiloxane marketed under the name "VOLATILE SILICONE 7158" by UNION CARBIDE, "SILBIONE 70045 V 5" by RHODIA, and mixtures thereof.

On peut également citer les mélanges de silicones cycliques avec des composés organiques dérivés du silicium, tels que le mélange d'octaméthylcyclotétrasiloxane et de tétratriméthylsilylpentaérythritol (50/50) et le mélange d'octaméthylcyclotétrasiloxane et d'oxy-1,1'-(hexa-2,2,2',2',3,3'-triméthylsilyloxy) bis-néopentane ; (ii) les silicones volatiles linéaires ayant 2 à 9 atomes de silicium et possédant une viscosité inférieure ou égale à 5.10-6m2/s à 25 °C. Il s'agit, par exemple, du décaméthyltétrasiloxane commercialisé notamment sous la dénomination "SH 200" par la société TORAY SILICONE. Des silicones entrant dans cette classe sont également décrites dans l'article publié dans Cosmetics and toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics ".Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the "VOLATILE SILICONE FZ 3109" marketed by UNION CARBIDE, of chemical structure:

Mention may also be made of cyclic silicone mixtures with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1 '- (hexa) -2,2,2 ', 2', 3,3'-trimethylsilyloxy) bis-neopentane; (ii) linear volatile silicones having 2 to 9 silicon atoms and having a viscosity of less than or equal to 5 × 10 -6 m 2 / s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by Toray Silicone. Silicones in this class are also described in the article published in Cosmetics and toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics ".

Non-volatile silicones that may be mentioned include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanes modified with organofunctional groups, and mixtures thereof.

The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

• des groupements polyéthylèneoxy et/ou polypropylèneoxy comportant éventuellement des groupements alkyle en C6-C24 tels que les produits dénommés diméthicone-copolyol commercialisé par la société DOW CORNING sous la dénomination DC 1248 ou les huiles SILWET® L 722, L 7500, L 77, L 711 de la société UNION CARBIDE et l'alkyl(C12)-méthicone-copolyol commercialisée par la société DOW CORNING sous la dénomination Q2 5200 ;
• des groupements thiols, comme les produits commercialisés sous les dénominations "GP 72 A" et "GP 71" de GENESEE ;
• des groupements alcoxylés, comme le produit commercialisé sous la dénomination "SILICONE COPOLYMER F-755" par SWS SILICONES et ABIL WAX® 2428, 2434 et 2440 par la société GOLDSCHMIDT ;
• des groupements hydroxylés, comme les polyorganosiloxanes à fonction hydroxyalkyle décrits dans la demande de brevet français FR-A-85 16334 .
• des groupements acyloxyalkyle tels que, par exemple, les polyorganosiloxanes décrits dans le brevet US-A-4957732 .
• des groupements anioniques du type acide carboxylique comme, par exemple, dans les produits décrits dans le brevet EP 186 507 de la société CHISSO CORPORATION, ou du type alkyl-carboxylique comme ceux présents dans le produit X-22-3701E de la société SHIN-ETSU ; 2-hydroxyalkylsulfonate ; 2-hydroxyalkylthiosulfate tels que les produits commercialisés par la société GOLDSCHMIDT sous les dénominations "ABIL® S201" et "ABIL® S255".
• Les huiles de silicone utilisables dans les compositions selon l'invention sont des polyméthylsiloxanes volatiles ou non, à chaîne siliconée linéaire ou cyclique, liquides ou pâteuse à température ambiante, notamment les cyclopolydiméthylsiloxanes (cyclométhicones) telles que la cyclohexasiloxane ; les polydiméthylsiloxanes comportant des groupements alkyle, alcoxy ou phényle, pendant ou en bout de chaîne siliconée, groupements ayant de 2 à 24 atomes de carbone ; les silicones phénylées comme les phényltriméthicones, les phényldiméthicones, les phényltriméthylsiloxydiphényl-siloxanes, les diphényl-diméthicones, les diphénylméthyldiphényl trisiloxanes, les 2-phényléthyltriméthyl-siloxysilicates, les polyméthyl-phénylsiloxanes ; et leurs mélanges.

Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising:

• polyethyleneoxy and / or polypropyleneoxy groups optionally containing C6-C24 alkyl groups such as the products known as dimethicone-copolyol sold by the company Dow Corning under the name DC 1248 or the oils SILWET® L 722, L 7500, L 77, L 711 of the company UNION CARBIDE and the alkyl (C12) -methicone-copolyol marketed by the company Dow Corning under the name Q2 5200;
• thiol groups, such as the products sold under the names "GP 72 A" and "GP 71" from GENESEE;
• alkoxylated groups, such as the product marketed under the name "SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX® 2428, 2434 and 2440 by the company GOLDSCHMIDT;
• hydroxyl groups, such as the hydroxyalkyl-functional polyorganosiloxanes described in the French patent application FR-A-85 16334 .
• acyloxyalkyl groups such as, for example, the polyorganosiloxanes described in the patent US Patent 4957732 .
• anionic groups of the carboxylic acid type such as, for example, in the products described in the patent EP 186,507 from the company CHISSO CORPORATION, or of the alkyl-carboxylic type, such as those present in the product X-22-3701E from the company Shin-Etsu; 2-hydroxyalkylsulfonate; 2-hydroxyalkylthiosulphate such as the products marketed by GOLDSCHMIDT under the names "ABIL® S201" and "ABIL® S255".
• The silicone oils that can be used in the compositions according to the invention are volatile or nonvolatile polymethylsiloxanes, with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl-dimethicones, diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethylsiloxysilicates, polymethylphenylsiloxanes; and their mixtures.

The silicone gums that can be used in the compositions according to the invention are polydiorganosiloxanes with a high molecular mass of between 200,000 and 2,000,000, used alone or as a mixture in a solvent chosen from volatile silicones, polydimethylsiloxane oils and polymethylphenylsiloxane oils. , polydiphenyldimethylsiloxane oils, isoparaffins, methylene chloride, pentane, hydrocarbons or mixtures thereof.

A silicone gum having a molecular weight of less than 1,500,000 is preferably used. The silicone gums are, for example, polydimethylsiloxanes, polyphenylmethylsiloxanes, poly (diphenylsiloxane dimethylsiloxanes), poly (dimethylsiloxanemethylvinylsiloxanes), poly (dimethylsiloxanephenylmethylsiloxanes), poly (diphenylsiloxane dimethylsiloxanemethylvinylsiloxanes).

These silicone gums can be terminated at the end of the chain by trimethylsilyl or dimethylhydroxysilyl groups.

The silicone resins that can be used in the compositions according to the invention are crosslinked siloxane systems containing the R ₂ SiO _2/2 , RSiO _3/2 , SiO _{4/2 units} , in which R represents a hydrocarbon group having from 1 to 6 atoms. carbon or a phenyl group. Among these products, those that are particularly preferred are those in which R denotes a lower alkyl radical (C ₁ -C ₆ ) or a phenyl radical.

The concentration of silicone or non-silicone fatty substances used in the compositions (iv) according to the present invention is between 0.01 and 20% and preferably between 0.05 and 10% by weight relative to the total weight of the composition. .

Composition (iv) may contain any additional ingredients of the composition ii.

Preferably, the care composition iv is applied before step i and is optionally rinsed. If it is flushed, its break time is between 30 seconds and 10 minutes.
The present invention is illustrated by the following examples. The contents are indicated in active matter.

Examples

The method for treating hair fibers according to the invention is implemented using a reducing composition and a care composition. <u> Reducing Composition B </ u> cysteine 4 g hydroxypropyl 0.5 g Mexomere PO 2.5g monoethanolamine qsp pH 9.2 Water qsp 100g Cetearyl alcohol 1.5g Steareth-20 0.5 WACKER-BELSIL ADM LOG 1 13.5 Water qsp 100g The method for treating hair fibers according to the invention is implemented using, as a means of raising the temperature, either a hair dryer or an iron.

1) Example of process with hairdryer

This method has the advantage of being fast and not very technical, which allows the model to apply it.

The hair (medium wavy natural hair) is washed with a standard shampoo and then wrung out.

Care D is applied immediately on the tips, without rinsing, at room temperature (22 ° C).

The reducing composition B is subsequently applied to the whole of the hair, by hand or by brush. A break time of 20 minutes, at room temperature, is respected, then the hair is rinsed with water abundantly.

Care D is applied on the whole of the hair and the hair is pre-dried with the hair dryer. Then a thorough blow-drying of the whole hair, always with a hair dryer and a brush, at a temperature of about 60 ° C.

In the end, the hair is smooth, without frizz and the fibers are easy to comb and untangle. The hair is not degraded.

Over the next few days, up to about 8 shampoos, the hair remains easier to comb, with less frizz and looser curls. The blow dry is fast and easy.

2) Example of a process with iron

This method is more technical than the previous one, but it has the advantage of a smoother result and a little more remanent, while being reversible.

The hair (medium wavy natural hair) is washed with a standard shampoo and then wrung out.

Care D is applied immediately on the tips, without rinsing, at room temperature (22 ° C).

The reducing composition B is subsequently applied to the whole of the hair, by hand or by brush. A break time of 20 minutes, at room temperature, is respected, then the hair is rinsed with water abundantly.

Care D is applied on the whole of the hair and the hair is pre-dried with the hair dryer. Careful smoothing of the entire hair is then performed with a flat iron whose temperature is 180 ° C.

The hair is smooth, without frizz and the fibers are easy to comb and untangle.

Over the next few days, up to about 10 shampoos, the hair remains easier to comb, with less frizz and looser curls. Daily brushing is fast and easy.

The hair is not degraded and the residual odor is weak.

Claims (10)

A method of shaping hair fibers comprising the steps of: (i) application to the hair fibers of a reducing composition, comprising one or more cationic polymers, the ratio of the weight concentration of the reducing agent to the concentration by weight of the cationic polymer being between 0.1 and 10, this application being followed by rinsing, (ii) applying a care composition, preferably not rinsed, comprising one or more amino silicones, (iii) raising the temperature of the capillary fibers by means of a heating means to a temperature of between 50 and 280 ° C., the rise in temperature being carried out before or after the possible rinsing of the hair fibers . Process according to Claim 1, characterized in that the ratio of the concentration by weight of the reducing agent to the concentration by weight of the cationic polymer is between 0.5 and 8, and more preferably between 1 and 5. Process according to either of Claims 1 and 2, characterized in that the cationic polymer used in stage (i) is chosen from cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium, such as homopolymers or copolymers. having as the main constituent of the chain of the units corresponding to formulas (V) or (VI):

formulas in which k and t are equal to 0 or 1, the sum k + t being equal to 1;
R ₉ denotes a hydrogen atom or a methyl radical;
R ₇ and R ₈ , independently of each other, denote an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group. (C ₁ -C ₄ ), or R ₇ and R ₈ may designate, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R ₇ and R _8, independently of one another, preferably denote an alkyl group having from 1 to 4 carbon atoms;
Y ^- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. Process according to either of Claims 1 and 2, characterized in that the cationic polymer used in step (i) is chosen from quaternary diammonium polymers containing recurring units corresponding to formula (VII):

formula (VII) in which: R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 6 carbon atoms or lower hydroxyalkylaliphatic radicals, or R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , together or separately, together with the nitrogen atoms to which they are attached, constitute heterocycles optionally containing a second heteroatom other than nitrogen or R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ represent a linear or branched C ₁ -C ₆ alkyl radical, substituted with a nitrile, ester, acyl, amide group or -CO-OR ₁₄ -D or -CO-NH-R ₁₄ -D wherein R ₁₄ is alkylene and D is a quaternary ammonium group; A1 and B1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more carbon atoms; oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and X ^- denotes an anion derived from a mineral or organic acid; A1, R ₁₀ and R ₁₂ may form with the two nitrogen atoms to which they are attached a piperazine ring; in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also designate a group

- (CH ₂ ) _n -CO-D-OC- (CH ₂ ) n-

in which n is between 1 and 100 and preferably between 1 and 50, and D is: a) a glycol residue of formula: -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas:

- (CH ₂ -CH ₂ -O) _x -CH ₂ -CH ₂ -

- [CH ₂ -CH (CH ₃ ) -O] _y -CH ₂ -CH (CH ₃ ) -

where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or the divalent radical

-CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -;

d) a ureylene group of formula: -NH-CO-NH-. Process according to any one of the preceding claims, characterized in that the concentration of reducing agent in the composition of step (i) is between 0.1% and 5% relative to the total weight of the composition. Process according to any one of the preceding claims, characterized in that the concentration of cationic polymer (s) in the composition of step i is (s) from 0.01 to 10% by weight. preferably from 0.1 to 5% by weight, relative to the total weight of the composition. Process according to any one of the preceding claims, characterized in that the temperature of the capillary fibers is raised to a temperature of between 80 ° C and 220 ° C in step (iii). Process according to any one of the preceding claims, characterized in that a thiolated reducing agent is used in stage (i). Process according to one of the preceding claims, characterized in that an aminosilicone corresponding to formula I is used as the amino silicone in the care composition (ii):

wherein x 'and y' are molecular weight dependent integers, generally such that said weight average molecular weight is from about 5,000 to about 500,000;
R1, R2, R3, which may be identical or different, denote a hydroxyl radical, a C1-C4 alkyl radical or a C1-C4 alkoxy radical, phenyl;
X denotes a C 1 -C 4 alkylene radical, branched or unbranched;
R4 denotes a C1-C4 alkyl or phenyl radical;
p, p 'denote independently of one another an integer ranging from 1 to 10. Process according to any one of the preceding claims, characterized in that the process further comprises the application of a care composition (iv) different from the care composition (ii) comprising the amino silicone, this composition comprising at least one silicone fatty substance or not